CN1187401C - Modified cationic starch composition for removing particles from aqueous dispersions - Google Patents

Modified cationic starch composition for removing particles from aqueous dispersions Download PDF

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Publication number
CN1187401C
CN1187401C CNB988108232A CN98810823A CN1187401C CN 1187401 C CN1187401 C CN 1187401C CN B988108232 A CNB988108232 A CN B988108232A CN 98810823 A CN98810823 A CN 98810823A CN 1187401 C CN1187401 C CN 1187401C
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starch
pam
boiling
cationic
charged ion
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CN1278282A (en
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R·H·莫菲特
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from US08/960,648 external-priority patent/US5859128A/en
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Modified starches prepared by cooking an amphoteric or cationic starch and certain polyacrylamides have improved performance in paper making if a soluble aluminum compound also is present.

Description

The intermittent pulp proportioning that contains treated starch
Background of invention
Invention field
The present invention relates to the composition that obtained by with positively charged ion or amphoteric starch and positively charged ion, negatively charged ion, nonionic or amphiprotic polyacrylamide boiling together.Resulting modified starch composition has as clarification aid to be removed the general use of solids and has in paper is made special purpose as retention aid from water dispersion.
The prior art background
The paper manufacture method comprises and forms mainly the paper web of being made up of cellulose fiber peacekeeping mineral filler and make it to dewater.This paper web forms by the following method: the aqeous suspension that will contain cellulose fiber peacekeeping mineral filler spreads in wire cloth or the netting, removes then and anhydrates to form web of fiber or page.Aqeous suspension is known as " intermittent pulp proportioning " at commercial field, and the water of telling is known as " plain boiled water ".
For a long time, industrially seeking the percentage ratio that various approach reduce the little cellulose fiber peacekeeping filler particles of volume always, both when forming paper web along with plain boiled water is removed together.Not only this means and lost raw material, and can gather the raw material that is known as " negatively charged ion refuse " in plain boiled water, the latter can hinder the efficient operation of equipment.Therefore, short grained improvement is kept removing of water is become easily, and has improved yield and the productivity in the paper technology.
Many in the prior art additives are proposed and improve keeping and the wet end dehydrating effect of fine particle (fines).Cationic starch is generally used for this purpose, particularly expensive cationic potato and waxy corn starch.Once also use not too expensive cationic corn starch, but generally can't provide enough fine particles to keep effect and wet end dehydrating effect.
Many suggestions that involve the efficient of improving the cationic starch that is used for this purpose have been proposed in the prior art. US patent 4,066,495 discloses a kind of manufacturing and has contained sun from flat starch and anion pp acyl The method of the paper of the anionic retention aids of amine polymerPCT application WO91/07543 (publications on May 30th, 1991) suggestion is cationic starch, and cationic polyacrylamide and polymeric silicicacid join in the cellulose suspension keeping and dewater with the improvement fine particle.Yet the interpolation of relatively large polyacrylamide not only makes paper technology increase cost, and intermittent pulp proportioning is too flocculated, and causes relatively poor paper to be shaped.
Therefore, still a kind of additive of demand improve fine particle in the paper manufacturing keep effect and wet end dehydrating effect.
Summary of the invention
Have now found that, if both sexes and cationic starch are with positively charged ion, negatively charged ion, nonionic or amphiprotic polyacrylamide boiling and add in the paper pulp that contains certain aluminum compound, both sexes and cationic starch are used as in the paper manufacturing to be kept auxiliary agent and will demonstrate improved performance.Therefore, the invention provides a kind of intermittent pulp proportioning, it contains:
(a) soluble aluminum compound, its amount are about 0.005-2.5 kilogram Al 2O 3/ metric ton dried paper and
(b) treated starch, by with at least a substitution value between about 0.01-0.2 both sexes or the aqueous solution of cationic starch and substitution value between 1wt%-80wt%, molecular weight at least 500,000 at least a nonionic or amphiprotic polyacrylamide, or the boiling and making together of positively charged ion or anionic polyacrylamide, precondition is:
(i) for the situation of selecting positively charged ion or non-ionic polyacrylamide, boiling is carried out being higher than under 7.0 the pH;
(ii) for the situation of selecting both sexes or anionic polyacrylamide, boiling can not make cationic starch neutralize more than 75%; With
(iii) the weight ratio of starch and polyacrylamide is higher than about 2: 1.
Sum up, the invention provides a kind of intermittent pulp proportioning, contain:
(a) soluble aluminum compound, its amount are 0.005-2.5 kilogram Al 2O 3/ metric ton dried paper and
(b) treated starch, by with at least a substitution value the aqueous solution of both sexes between the 0.01-0.2 or cationic starch and substitution value between 1wt%-80wt%, molecular weight at least 500,000 at least a nonionic or amphiprotic polyacrylamide, or the boiling and making together of positively charged ion or anionic polyacrylamide, precondition is:
(i) for the situation of selecting positively charged ion or non-ionic polyacrylamide, boiling is carried out being higher than under 7.0 the pH;
(ii) for the situation of selecting both sexes or anionic polyacrylamide, boiling makes the charge neutralization of cationic starch be less than 75%;
If (iii) the anionic polyacrylamide molecular weight is low, then boiling makes and is less than 75% cationic starch electric charge and is neutralized, if anionic polyacrylamide molecular weight height, then boiling makes and is less than 50% cationic starch electric charge and is neutralized, said low for being low to moderate 500,000, height is up to 8,000,000; With
(iv) the weight ratio of starch and polyacrylamide is higher than 2: 1.
Embodiment be wherein cationic starch with the cation acrylamide boiling.
Embodiment be wherein cationic starch with the boiling of negatively charged ion acrylamide.
Embodiment is wherein before adding treated starch, and soluble aluminum compound is joined in the paper pulp.
An embodiment is that wherein starch is selected from W-Gum, yam starch and waxy corn starch.
An embodiment is wherein also to have colloid silica.
An embodiment is wherein also to have anionic inorganic colloid.
An embodiment is that wherein soluble aluminum compound is selected from Tai-Ace S 150, aluminate, aluminum nitrate, poly aluminium chloride and poly aluminium sulfate.
Being described in detail of preferred embodiment
What treated starch had improved fine particle in the paper technology keeps effect and wet end dehydrating effect, can select some additive not too expensive or that reduce consumption simultaneously.More particularly, have now found that, when with positively charged ion, negatively charged ion, nonionic or amphiprotic polyacrylamide boiling, positively charged ion or amphoteric starch have improved the effect of keeping of fine particle, when being used in combination with certain aluminum compound, effect has surpassed in paper technology and separately starch and polyacrylamide has been added the effect that is reached.
Starch
Cationic starch can be any those products that are used for papermaking in the past.Cationic starch can obtain from any common starch generation raw material such as W-Gum, yam starch, waxy corn starch and wheat starch.Realize cationization by industrial known any method, as adding the cationic starch that 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride obtains to have various nitrogen substitution values.Positively charged ion substitution value on the starch (wt% nitrogen/starch) can be in about 0.2 scope of about 0.01-, preferably between 0.02-0.15.Amphoteric starch such as the yam starch that also can select nature to exist, or synthetic amphoteric starch.
Polyacrylamide (PAM)
PAM is nonionic, both sexes, anionic or preferred cationic type, molecular weight at least 500,000, preferably at least 1,000,000.
It is about 80% for 1%-that positively charged ion and both sexes PAM have positively charged ion substitution value (by wt), preferred 10%-about 40%." substitution value " is meant that polymkeric substance contains the random repeated monomer unit of being with the chemical functional group, this functional group's band cationic charge when soluble in water.These monomeric units include but not limited to the group of amine and so on.PAM can be a solid, powder type, microballon form, water-in-oil emulsion or any other industrial form known.Suitable PAM can be from AlliedColloids, Suffolk VA and from Nalco, and Naperville IL, and other source obtains.
Have now found that negatively charged ion PAM should have 500,000-20,000,000, more preferably 1,000,000-15,000,000 molecular weight.Negatively charged ion PAM should have about 1-80wt% and the more preferably anionization degree of 2-70wt%.Generally, low anionization degree PAM makes more PAM obtain higher levels of ash retention with the starch boiling before surpassing 75% by the dosis neutralisata at the starch electric charge.Find that also general higher molecular weight PAM will obtain the ash retention of higher level.
Negatively charged ion PAM contains carboxylate radical, and sulfonate radical, or other common anion group replace the amine or other cation group that are contained in the cationic PAM.As an example, wherein acrylamide/Acrylic Acid Monomer weight ratio is that 90/10 acrylamide and acrylic acid multipolymer have 10% substitution value.PAM can be a solid, powder type, microballon form, water-in-oil emulsion or any other industrial known form.Suitable PAM can be from Allied Colloids, Suffolk, and Virginia and from Nalco, Naperville Illinois, and other source obtains.
Boiling
Starch and PAM can do mixed or the slurry form blending of conduct in water together before the boiling, or their blending in the starch cook process.If not do to mix or made the PAM of slurry, this PAM also can with starch blending and boiling before carry out pre-hydration.If not do the starch that mixes or made slurry, this starch also can carry out boiling, with PAM blending and and then boiling.
Boiling can use the starch cook device to finish in the paper mill easily.Can select batch digester or continuous steamer such as jet flow (jet) pulp digester.Continuously jet flow boiling typical case under about 80-130 ℃ the temperature at 1 normal atmosphere or more carry out under the high pressure.Solids content generally is lower than 15% in digestion process, still, if can realize sufficient mixing, then also can use higher solids concn.
Selected cooking time and temperature will change with composition and equipment.Conditions of cooking must be enough to make the starch gel gel and make PAM portion water merging and starch reaction at least.For this purpose, typically select to be higher than 65 ℃, preferred 80-100 ℃ high temperature is though also can select to be lower than 65 ℃ temperature for some compositions and digesting apparatus.For example, advantage of the present invention is observed being low to moderate under 60 ℃ the boiling temperature.If prevented the decomposition of starch and PAM, then can select to be higher than 100 ℃ temperature.Therefore,, be higher than under the atmospheric pressure, using to be higher than 100 ℃ and up to 130 ℃ or higher boiling temperature implementing to select batch cooking when of the present invention.Selected cooking time typically at several minutes to less than 1 hour.Generally need longer cooking time for lower boiling temperature.
When using positively charged ion or nonionic PAM, if boiling can obtain optimum to starch/PAM mixture under 7 the pH value being higher than, although be lower than some improvement of also finding under 7 the pH value on ash retention.Positively charged ion or nonionic PAM and starch preferred boiling pH separately is about 8-about 10.5.When selecting negatively charged ion or both sexes PAM, the pH value is not crucial, but typically in the 3-11 scope.
Boiling pH can regulate with acid, alkali or the salt of routine.It is useful especially that the use of alkalescence aluminum compound such as sodium aluminate and potassium has been found for this purpose, because these compounds have also strengthened retention performance, this will describe in embodiment 6.Astoundingly, retention performance even in acid intermittent pulp proportioning, also be improved.In addition, have now found that, in cooking liquor, comprise the starch that alkaline aluminum compound will obtain modification, the feasible microgranular retention aid that can in acid intermittent pulp proportioning, use non-calorize, further improve retention performance, and the retention aid of these non-calorizes is not brought into play its effect usually in acid paper pulp.
The weight ratio of PAM and starch will with selected composition and fine particle keep and the wet end dehydration aspect improved degree change.For example, have now found that the W-Gum of poor performance can be improved to the degree that equals or be superior to more expensive yam starch, this is by W-Gum is realized with little PAM boiling to 1wt%.Typically, the weight ratio of selected starch and PAM will be higher than 2: 1, preferred 5: 1.The amount of adding the PAM in the starch to should be restricted to the amount that causes starch sedimentation that is lower than, and it changes with selected composition and boiling method.If select negatively charged ion or both sexes PAM, very crucial is, and conditions of cooking (being PAM anionization degree, the ratio of PAM and starch, the cation ionization degree of starch) will be limited in that feasible 75% the starch electric charge of being no more than is neutralized.Otherwise performance will suffer damage.
Papermaking
The starch of boiling/PAM composition can be used as retention aid and joins in any suitable intermittent pulp proportioning to improve fine particle and keep effect and wet end drainage effect.Intermittent pulp proportioning contains various wood pulps and mineral filler, typically has the pH value of about 4-10.So the kraft pulp of bleaching, thermomechanical pulp, CTMP and ground wood pulp can use with clay, precipitation or water-ground limestone, titanium dioxide and other mineral filler, if desired.This filler typically uses with 15%-20% consumption (according to the weight percentage of total paper weight), but can reach high to 30% or higher amount for some special applications.
According to the present invention, the PAM/ starch composites of boiling is added in the intermittent pulp proportioning that contains certain aluminum compound, or joins in the intermittent pulp proportioning that will add these aluminum compounds subsequently.Aluminum compound has strengthened the performance of boiling PAM/ starch.Aluminum compound generally is present in the intermittent pulp proportioning with solubilized form, and can be used as solution or granular solids interpolation.Preferably, at first add aluminum compound, add the PAM/ starch composites of boiling then.
Tai-Ace S 150, aluminate (for example sodium aluminate or potassium), aluminum nitrate, poly aluminium chloride, or poly aluminium sulfate all is more satisfactory selection.Also can select to dissolve in other aluminum compound in the paper pulp.Dosage is typically at the about 5 pounds of Al of 0.01- 2O 3/ ton dried paper (0.005-2.5 kilogram/metric ton).
When intermittent pulp proportioning also contains anionic inorganic colloid commonly used in the paper industry, obtained special ideal effect.Therefore, intermittent pulp proportioning can contain for example montmorillonite, wilkinite, and silica gel, aluminum modified silica, pure aluminium silicate colloidal sol, poly-silicic acid, polysilicate microgels and poly-silico-aluminate microgel are used alone or as a mixture.
This intermittent pulp proportioning also can contain other typical additive, as sizing agent, and cationic polymers (retention aid and flocculation agent), anionic polymer, and/or add starch separately.Although mentioned component adds by any order good result is arranged all, preferred interpolation is at first to add aluminum compound in proper order, then adds the starch/PAM of boiling, adds the inorganic anion colloid then.
Although the present invention at length is described for papermaking, should be realized that composition also can be used as finings so that help removing solids from aqeous suspension.
The present invention is illustrated by the following examples, but the present invention is not constituted qualification.
For consistence, in all embodiments the performance of test soln be with 5g retention aid/L by 35% bleached sulphate hard wood pulp, the intermittent pulp proportioning that 35% bleached sulphate soft wood pulp and 30% precipitated chalk (PCC) are formed is measured.Intermittent pulp proportioning mixes under 750RPM in the Britt Jar that 50R sieve (100 order) is housed.According to Tappi standard T-261, from plain boiled water sample determination ash retention.
Embodiment 1
How this embodiment has illustrated cationic starch and cationic PAM boiling together to obtain than same two kinds of chemical separately but add in the intermittent pulp proportioning better retention simultaneously to.By being that the cationic PAM " A " of 22wt% is mixed and prepared dried blend available from the Stalok 300 cationic corn starch of Staley Starch and 0.04g molecular weight about 4,000,000 and substitution value with 3.0g.This blend is added in the 497g deionized water, with sodium hydroxide with pH regulator to 8.5.This solution heated 30 minutes on the hot plate agitator, came to life in the time of about 15 minutes and entered digester cycle.After boiling, take off solution, allow its cooling from hot plate.This solution is weighed again, and any water of compensation institute's evaporable.
By being mixed with 0.04gPAM " A " available from the BMB-40 cationic potato starch of Akzo Nobel, 3.0g prepares second kind of dried blend.In this blend, add the 497g deionized water and regulate pH value to 8.5, carry out boiling according to foregoing method.
Thing as a comparison, according to above-described method, Stalok 300 W-Gums and BMB-40 yam starch prepare as 0.5wt% solution form.The pH value of these starch solutions is not regulated.By 1g PAM " A " being joined the 799g deionized water and then resulting solution being mixed the 0.125wt% sample that prepared PAM " A " in 1 hour separately.
Starch and PAM join in the intermittent pulp proportioning with the dosage of 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound/ton (0.125 kilogram/tonne) respectively.This embodiment and below among the embodiment, in some tests, according to US5,482,693 prepared poly-silico-aluminate microgel solution (PAS) are added in the intermittent pulp proportioning.The interpolation of chemical is in proper order:
Time (second) Step
00 Start mixing machine
15 Add starch; Add PAM
30 Add PAS
45 Open Britt Jar water discharge valve
50 Begin to collect plain boiled water
80 Stop to collect plain boiled water
Ash content is kept effect and is shown in Table 1.
Table 1
% ash retention vs adds program and PAS dosage
PAS dosage (kilogram SiO 2/ metric ton) Add W-Gum+PAM separately Both boilings of W-Gum+PAM Add yam starch+PAM separately Both boilings of yam starch+PAM
0 17％ 27％ 21％ 25％
0.5 27％ 39％ 40％ 47％
1.0 28％ 44％ 47％ 56％
The result clearly illustrates that, before joining cationic starch and two kinds of chemical of cationic PAM in the intermittent pulp proportioning with both together boiling can improve ash retention significantly, ash retention improves with the raising of PAS dosage.Especially embody from composition-cost viewpoint, the performance of W-Gum and PAM is equal to the performance of the more expensive yam starch/PAM binding substances that adds separately in the prior art basically when boiling together.
Embodiment 2
This embodiment has illustrated with cationic starch and cationic PAM boiling together rather than with they blended necessity at low temperatures simply.
Prepare sample A by mixing 3.0g Stalok 300 and 497g deionized water and regulating pH value to 8.5 then.This solution carries out boiling by using the cooking procedure described in the embodiment 1.After sample is cooled to 35 ℃, add the PAM " A " of 0.04g, resulting solution before test mixed 1 hour.
Prepare sample B by mixing 3.0g Stalok 300 and 497g deionized water and regulating pH value to 8.5 then.This solution carries out boiling by using the cooking procedure described in the embodiment 1.After sample is cooled to 95 ℃, add the PAM " A " of 0.04g, resulting solution before test mixed 1 hour.
Prepare sample C by mixing the PAM " A " of 3.0g Stalok 300 and 0.04g, adding the 497g deionized water then and regulate pH value to 8.5 then.This solution carries out boiling by using the cooking procedure described in the embodiment 1.
Following table 2 shows ash content and keeps effect.In this table, the pH value of starch solution or starch/PAM solution before boiling is denoted as " a:pH ".Also measure the pH value after boiling, and be designated as " b:pH ".
Table 2
% ash retention vs boiling/combination process and PAS dosage
PAS dosage (kilogram SiO 2/ metric ton) Stalok 300 and PAM " A "
Sample A Sample B Sample C
a：pH＝8.5 b：pH＝7.0 a：pH＝8.5 b：pH＝8.1 a：pH＝8.5 b：pH＝9.2
0 25％ 29％ 36％
0.5 39％ 44％ 55％
The result also shows, be higher than independent boiling cationic starch 8.5 times at pH, mix down less than not improving ash retention fully effectively at 35 ℃ (biased sample A) or 95 ℃ (biased sample B) then with PAM, with the method according to this invention with their boilings Comparatively speaking (cooked sample C).
Embodiment 3
This embodiment has illustrated that the pH value plays an important role for improved retention when boiling cationic starch and cationic PAM together.At first, the Stalok 300 W-Gum samples of 3.0g and the blending of the various types of cationic PAM dry method of 0.04g are dispersed in the 497g deionized water then.Cationic PAM " B " has the substitution value of about 7,000,000 molecular weight and 22wt%.Positively charged ion (liquid) PAM " C " has the substitution value of about 4,000,000 molecular weight and 22wt%.Because PAM " C " has 50% active component content, adds 0.08g in this case.The pH value of starch/PAM solution is adjusted to the value shown in the table 3 (being designated as a:pH) then, and carries out boiling by the cooking procedure described in the embodiment 1.NA is meant that pH does not regulate.Measure the pH after the boiling, and be designated as " b:pH ".
As before, above-mentioned solution is as the tested performance of retention aid.Starch and PAM join in the paper pulp with the dosage of 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound (0.125 kilogram/tonne) respectively.In some tests, the PAS that makes by embodiment 1 is added in the paper pulp.Identical among the interpolation of chemical order and the embodiment 1.The results are shown in the table 3.
Table 3
% ash retention vspH regulates and PAS dosage
PAS dosage (kilogram SiO 2/ metric ton) A.Stalok 300 and PAM " A "
a：pH＝NA b：pH＝4.9 a：pH＝7.0 b：pH＝6.4 a：pH＝8.5 b：pH＝8.0 a：pH＝10.0 b：pH＝9.7
0 22％ 25％ 30％ 29％
0.5 30％ 37％ 44％ 47％
1.0 31％ 40％ 43％ 48％
PAS dosage (kilogram SiO 2/ metric ton) B.Stalok 300 and PAM " B "
a：pH＝NA b：pH＝5.1 a：pH＝7.0 b：pH＝6.9 a：pH＝8.5 b：pH＝8.9 a：pH＝10.0 b：pH＝10.1
0 20％ 28％ 32％ 30％
0.5 29％ 46％ 42％ 51％
PAS dosage (kilogram SiO 2/ metric ton) C.Stalok 300 and PAM " C "
a：pH＝NA b：pH＝5.4 a：pH＝7.5 b：pH＝7.0 a：pH＝8.5 b：pH＝9.0 a：pH＝10.0 b：pH＝10.0
0 22％ 27％ 27％ 30％
0.5 29％ 45％ 46％ 44％
1.0 33％ 44％ 48％ 43％
The result clearly illustrates that and is being higher than under 5.5 the pH value by cationic starch and cationic PAM boiling have together been improved the rate of staying significantly.
Embodiment 4
This embodiment is used for illustrating that the cationic starch with pre-hydrated cationic PAM blending and boiling under pH8.5 also improves retention.By in the 799g deionized water, adding the sample that 1.0g PAM " B " can prepare 0.125% cationic PAM.Allow this solution generation hydration reach 1 hour.This 0.125% PAM solution with 33.3g mixes with the deionized water of 464g and the Stalok 300 of 3.0g then.PH is adjusted to 8.5, according to the program described in the embodiment 1 solution is carried out boiling.By with the PAM " B " of 0.04g with the Stalok 300 dry method blending of 3g with dried blend is joined prepare second kind of starch/PAM blend in the 497g deionized water then.PH is adjusted to 8.5, carries out boiling according to program described in the embodiment 1.
As before, above-mentioned solution is as the tested performance of retention aid.Dosage with 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound (0.125 kilogram/tonne) joins starch and PAM in the intermittent pulp proportioning respectively.In some tests, the PAS that makes among the embodiment 1 is joined in the paper pulp.The same among the interpolation of chemical order and the embodiment 1.Joined situation in the paper pulp separately and simultaneously for Stalok 300 cationic corn starch and pre-hydration PAM " B ", also tested.
Table 4
% ash retention vs PAM hydration and PAS dosage
PAS dosage (kilogram Si0 2/ metric ton) Add W-Gum+pre-hydration PAM separately W-Gum+both boilings of dry PAM Yam starch+pre-both boilings of hydration PAM
0 23％ 36％ 37％
0.5 37％ 51％ 51％
1.0 44％ 53％ 50％
Result shown in the table 4 clearly illustrates that cationic starch provides and the starch of this dry method blending of boiling and the retention of the same level of PAM with pre-hydration PAM boiling under pH8.5.Identical chemical is joined separately in the paper pulp, and two methods all provide excellent result.
Embodiment 5
This embodiment has illustrated in the papermaking batching and has added the performance that aluminum compound has strengthened cationic starch/cationic PAM blend.By being mixed with 0.04g cationic PAM " A " available from the Stalok 300 cationic corn starch of Staley Starch, 3.0g prepares dried blend.In this blend, add the 497g deionized water.PH is adjusted to 8.6.Solution heated 30 minutes on the hot plate agitator, came to life about 15 minutes and entered digester cycle.Solution is weighed again and is compensated any water of institute's evaporable after boiling.The final pH value of solution is 7.1.
As before, above-mentioned solution is as the tested performance of retention aid.Dosage with 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound (0.125 kilogram/tonne) joins starch and PAM in the intermittent pulp proportioning respectively.The PAS that makes by embodiment 1 is added in the paper pulp with 2 pounds/ton (1 kilograms/tonne).In some tests, paper grade (stock) alum and sodium aluminate are also joined in the paper pulp.Interpolation is in proper order:
Time (second) Step
00 Start mixing machine
15 Add aluminum compound
30 Add starch; Add PAM
45 Add PAS
60 Open Britt Jar water discharge valve
65 Begin to collect plain boiled water
95 Stop to collect plain boiled water
Table 5
% ash retention vs aluminium adds step
Aluminum type Aluminium dosage Ash retention
Pound/ton Kilogram/metric ton
Do not have 0 0 61％
Alum 0.5 0.25 64％
Alum 1.0 0.5 68％
Alum 2.0 1.0 72％
Sodium aluminate 0.5 0.25 72％
Sodium aluminate 1.0 0.5 72％
Sodium aluminate 2.0 1.0 73％
The result shows by add aluminum compound in intermittent pulp proportioning and has further improved retention.
Embodiment 6
This embodiment how to have illustrated before the boiling by use alkaline aluminum compound regulate cationic starch/cationic PAM to pH7 with on strengthen the usefulness of blend as retention aid.Mix by sodium aluminate and to prepare dried blend the PAM " B " of 3.0g Stalok 300 cationic corn starch and 0.04g and various amount (as listed in the table 7) for embodiment D to G.In these blends, add the 497g deionized water.The pH that does not contain the blend of sodium aluminate is adjusted to 8.5.The pH of blend that contains sodium aluminate is measured but do not regulate, and is designated as " a:pH ".This solution heated 30 minutes on the hot plate agitator and came to life 15 minutes and enter digester cycle.After boiling, solution is weighed again, and any water of compensation institute's evaporable.Measure the pH of solution once more and be designated as " b:pH ".
The same by the front, above-mentioned solution is as the tested performance of retention aid.Dosage with 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound (0.125 kilogram/tonne) joins starch and PAM in the intermittent pulp proportioning respectively.In some tests, the PAS that makes by embodiment 1 is added in the intermittent pulp proportioning.Identical among chemical addition sequence and the embodiment 1.
Table 6
% ash retention vs cooking procedure and PAS dosage
A. the method for preparing sample
Sample D Sample E Sample F Sample G
The sodium aluminate that adds, g 0 0.09 0.17 0.35
a：pH 8.5 9.1 9.6 10.1
b：pH 8.9 9.3 9.5 9.8
B. retention test-results
PAS dosage (kilogram SiO 2/ metric ton) Sample D Sample E Sample F Sample G
0 27％ 34％ 34％ 35％
0.5 48％ 56％ 60％ 64％
The result is clearly shown that the beneficial effect that uses alkaline aluminum compound to regulate the pH of cationic starch/cationic PAM blend.
Embodiment 7
This embodiment how to have illustrated with cationic starch and negatively charged ion PAM together 10 times boilings of pH obtained than will same two kinds of chemical separately but join better retention in the intermittent pulp proportioning simultaneously.By being mixed available from the nonionic PAM " D " of the molecular weight about 14,000,000 of the Stalok 300 cationic corn starch of Staley Starch and 0.04g, 3.0g prepares dry blend.In this blend, add the 497g deionized water.PH is adjusted to 10.1.This solution heated 30 minutes on the hot plate agitator and came to life about 15 minutes and enter digester cycle.After boiling, solution is weighed again and is compensated any water of institute's evaporable.The final pH of solution is 9.9.
As a comparison, according to above-described method, prepare the sample of Stalok300 with 0.5wt% solution form.The pH value of solution is measured at 7.5 and do not regulate.
Mix the 0.125wt% solution that prepared PAM " D " in 1 hour by interpolation 1g PAM " D " in the 799g deionized water and with resulting solution.PH value of solution is measured at 4.4 and do not regulate.
As before, above-mentioned solution is as the tested performance of retention aid.
Dosage with 15 pounds/ton (7.5 kilograms/tonne) and 0.25 pound (0.125 kilogram/tonne) joins starch and PAM in the intermittent pulp proportioning respectively.In some tests, the PAS that makes by embodiment 1 is added in the paper pulp.Identical among chemical addition sequence and the embodiment 1.
Table 7
% ash retention vs cooking procedure and PAS dosage
PAS dosage (kilogram SiO 2/ metric ton) Add W-Gum+nonionic PAM separately Both boilings together of W-Gum+nonionic PAM
0 11％ 22％
0.5 19％ 33％
1.0 22％ 33％
The result clearly illustrates that, before joining cationic starch and nonionic PAM in the intermittent pulp proportioning, by two kinds of chemical boiling have together been improved retention.
Embodiment 8-12
Among the embodiment 8-12 below, use Rank Brothers Charge AnalyserII (Britain Camb) streaming current detector to measure the electric charge requirement of cationic starch/negatively charged ion PAM blend.The electric charge requirement of alkaline kation starch and cationic starch/PAM blend is by measuring with poly-(vinyl sulfonic acid, sodium salt) solution titration 1.25g starch/PAM blend in the 225ml deionized water of 0.001N under pH8.If the electric charge on starch/PAM blend is determined to be negatively charged ion, then the charge neutralization percentage of starch is registered as and is higher than 100%.
Embodiment 8
This embodiment is that usefulness contains paper grade (stock) alum solution [Al2 (SO4) 318H2O] or the intermittent pulp proportioning of sodium aluminate carries out.This embodiment explanation, when cationic potato starch during with high molecular (MW) negatively charged ion PAM boiling, negatively charged ion PAM must neutralize and be lower than the electric charge of about 50% cationic starch, the performance of the starch/PAM solution of boiling is surpassed same chemical is joined the shown performance that goes out in the intermittent pulp proportioning separately.
By the substitution value with 2.5g is 0.042 Stalok 410 cationic potato starch (available from Staley Starches) and molecular weight about 8,000,000 and commodity negatively charged ion PAM with 12% anionization degree in deionized water together boiling prepare cationic starch/negatively charged ion PAM blend.The total mass of starch/PAM solution is 500g.Before cationic starch and additional water mixing and boiling, negatively charged ion PM carries out pre-hydration in 0.125wt% (by active substance).Starch/PAM blend heated 30 minutes on the hot plate of magnetic agitation, came to life about 20 minutes and entered digester cycle.
Carry out the retention test by the negatively charged ion PAM that uses 15 pounds (7.5 kilograms)/ton cationic potato starch and various dosage.In 10 seconds after in cationic starch and negatively charged ion PAM, adding, adds 2 pounds (1 kilograms)/ton (press SiO 2Meter) 4nm colloidal silica gel (available from Nalco).
The result shows, the boiling together of cationic starch and high MW negatively charged ion PAM, with only separately add same chemical Comparatively speaking, in salic intermittent pulp proportioning, produced excellent ash content and kept effect, wherein be lower than about 50% starch electric charge and neutralized by negatively charged ion PAM.Outcome record is in table 8.
Table 8
% ash retention vsPAM dosage and aluminum type
Ash retention %
% cationic starch charge neutralization rate PAM dosage (pound/ton) a The weight ratio of starch/PAM 0.5 pound (0.25 kilogram)/ton Al2O3 (as alum) 1 pound (0.5 kilogram)/ton Al2O3 (as alum) 0.5 pound (0.25 kilogram)/ton Al2O3 (as sodium aluminate)
Add separately/simultaneously Boiling together Add separately/simultaneously Boiling together Add separately/simultaneously Boiling together
11 0.25(0.125) 60/1 47 70 52 70 55 79
25 0.5(0.25) 30/1 49 55 58 59 61 68
53 0.75(0.375) 20/1 59 46 57 45 63 48
Numerical value in a bracket is kilogram/ton (kg/t).
Embodiment 9
Carry out this embodiment with the intermittent pulp proportioning that contains 0.5 (0.25 kilogram) pound/ton Al2O3 (as the paper grade (stock) alum solution).Embodiment has illustrated when cationic potato starch during with lower molecular weight (MW) negatively charged ion PAM boiling, negatively charged ion PAM can neutralize up to about 75% and still provide excellent ash content to keep effect, compares with the independent shown effect of same chemical of adding in intermittent pulp proportioning.
Be 0.04 BMB-40 cationic potato starch with the substitution value of 2.5g with the commodity negatively charged ion PAM with molecular weight about 1,000,000 and 8wt% anionization degree together in deionized water boiling prepare cationic starch/negatively charged ion PAM blend.Starch/PAM solution total mass is 500g.Cationic starch and negatively charged ion PAM are added in the deionized water as dry powder, heat 30 minutes on the magnetic agitation hot plate then.Solution seethed with excitement about 20 minutes and entered digester cycle.
Carry out the retention test by the negatively charged ion PAM that uses 20 pounds (10 kilograms)/ton cationic potato starch and various dosage.In 15 seconds after in cationic starch and negatively charged ion PAM, adding, adds 2 pounds (1 kilograms)/ton (press SiO 2Meter) 4nm colloidal silica gel (available from Nalco).
The result shows, the boiling together of cationic starch and low MW negatively charged ion PAM, with only separately add same chemical Comparatively speaking, in salic intermittent pulp proportioning, produced excellent ash content and kept effect, wherein be lower than about 75% starch electric charge and neutralized by negatively charged ion PAM.Outcome record is in table 9.
Table 9
% ash retention vs hangs down MW PAM dosage
% cationic starch charge neutralization rate PAM dosage (pound/ton) The weight ratio of starch/PAM Add separately/simultaneously Boiling together
22 0.7(0.35) 30/1 38 40
48 1.3(0.65) 15/1 35 41
55 2.7(0.235) 7.5/1 34 54
73 4(2) 3.8/1 29 50
＞100 5.3(2.65) 2.8/1 32 21
Numerical value in a bracket is kilogram/ton (kg/t).
Embodiment 10
With containing 0.5 pound (0.25 kilogram)/ton Al 2O 3The intermittent pulp proportioning of (as the paper grade (stock) alum solution) carries out this embodiment.The use of embodiment has illustrated low " S value " silicon sol and cationic potato starch, the latter is with high molecular (MW) negatively charged ion PAM boiling.
With Stalok 410 cationic potato starch of 2.5g and commodity negatively charged ion PAM with molecular weight about 1,000,000 and 40wt% anionization degree together in deionized water boiling prepare cationic starch/negatively charged ion PAM blend.Starch/PAM solution total mass be 500g. with cationic starch and additional water be mixed together with boiling before, negatively charged ion PAM is in 0.125wt% (by active substance) pre-hydration down.Starch/PAM blend heated 30 minutes on the magnetic agitation hot plate, came to life about 20 minutes and entered digester cycle.
Carry out the retention test by the negatively charged ion PAM that uses 20 pounds (10 kilograms)/ton cationic potato starch and various dosage.15 seconds after cationic starch and negatively charged ion PAM add simultaneously, add 1 pound (0.5 kilogram)/ton (presses SiO 2Meter) BMA-670 silicon sol (available from AkzoNobel) or 0.5 pound (0.25 kilogram)/ton (is pressed SiO 2Meter) Particol BX silicon sol (available from Allied Colloids).
The result shows, the boiling together of cationic starch and high MW negatively charged ion PAM, with only separately add same chemical Comparatively speaking, in salic intermittent pulp proportioning, produced excellent ash content and kept effect, wherein be lower than about 50% starch electric charge and neutralized by negatively charged ion PAM.Outcome record is in table 10.
Table 10
% ash retention vs high MW PAM dosage and low S value silicon sol
% cationic starch charge neutralization rate PAM dosage (pound/ton) The wt ratio of starch/PAM 1 pound of/ton BMA-670 0.5 pound/ton Particol BX
Add separately/simultaneously Boiling together Add separately/simultaneously Boiling together
18 0.2(0.1) 100/1 38 58 41 54
42 0.4(0.2) 50/1 41 46 40 40
59 0.6(0.3) 33/1 43 31 46 28
72 0.8(0.4) 25/1 48 24 48 23
Numerical value in a bracket is kilogram/ton (kg/t).
Embodiment 11
With containing 0.5 pound (0.25 kilogram)/ton Al 2O 3The intermittent pulp proportioning of (adding as poly aluminium chloride solution) carries out this embodiment.This embodiment has illustrated the bentonitic use of colloidal silica sol and hydration, and the latter is with high molecular (MW) negatively charged ion PAM boiling.
By be 0.036 Stalok 300 cationic corn starch with substitution value with the commodity negatively charged ion PAM with molecular weight about 8,000,000 and 5wt% anionization degree together in deionized water boiling prepare cationic starch/negatively charged ion PAM blend.Starch/PAM solution total mass is 500g.Mix with cationic starch and additional water and boiling before, negatively charged ion PAM is in down pre-hydration of 0.125wt% (by active substance).Starch/PAM blend heated 40 minutes on the magnetic agitation hot plate, came to life about 20 minutes and entered digester cycle.
Carry out the retention test by the negatively charged ion PAM that uses 20 pounds (10 kilograms)/ton cationic corn starch and various dosage.In 15 seconds after in cationic starch and negatively charged ion PAM, adding, adds 2 pounds (1 kilograms)/ton (press SiO 2Meter) 4nm colloidal silica gel or 5 pounds (0.25 kilogram)/ton hydration wilkinite (available from Allied Colloids).
The result shows, the boiling together of cationic starch and high MW negatively charged ion PAM has produced excellent ash content and has kept effect in salic intermittent pulp proportioning, with the same chemical of independent interpolation to the limit that experimentized Comparatively speaking (34% starch electric charge is neutralized by negatively charged ion PAM).Outcome record is in table 11.
Table 11
% ash retention vs high MW PAM dosage and anionic inorganic colloid
% cationic starch charge neutralization rate PAM dosage (pound/ton) The weight ratio of starch/PAM Ash retention %
2 pounds (1 kilogram)/ton 4nm colloidal silica 5 pounds (2.5 kilograms)/ton wilkinite
Add separately/simultaneously Boiling together Add separately/simultaneously Boiling together
27 0.75 (0.375) 27/1 34 51 27 37
34 1(0.5) 20/1 35 49 28 37
A is referring to the footnote a of table 8
Embodiment 12
By 40% bleached sulphate hard wood pulp, carry out this embodiment in the acid intermittent pulp proportioning that 40% bleached sulphate soft wood pulp and 20% clay are formed.Paper pulp pH is adjusted to 4.0.With 2 pounds (1 kilograms)/ton Al 2O 3Join in the intermittent pulp proportioning as paper-maker's alum solution.This embodiment shows how to allow alkaline aluminum compound further improve ash retention with cationic starch and negatively charged ion PAM boiling.
By Stalok 410 cationic potato starch of 2.5g and 0.083g had about molecular weight of 8,000,000 and the commodity negatively charged ion PAM of 12wt% anionization degree and the Al of 0.69g 2O 3(as sodium aluminate) together in deionized water boiling prepare cationic starch/negatively charged ion PAM/ alkali alumina blend.Mix with cationic starch and additional water and boiling before, the total mass of (by active substance).Starch/PAM blend heated 40 minutes on the magnetic agitation hot plate, came to life about 20 minutes and entered digester cycle.Only cationic starch/negatively charged ion PAM (does not have Al 2O 3) the boiling blend be found to have and be neutralized 16% cationic starch electric charge.
By using 20 pounds (10 kilograms)/ton cationic corn starch, 0.67 pound (0.335 kilogram)/ton negatively charged ion PAM and 0.55 pound (0.275 kilogram)/ton Al 2O 3(as sodium aluminate) carries out the retention test.At cationic starch, in 15 seconds after adding in the time of negatively charged ion PAM and sodium aluminate, adds 2 pounds (1 kilograms)/ton (press SiO 2The 5nm colloidal silicon sol (available from the BMA-9 of Akzo Nobel) of surface aluminateization meter).
The result shows that the boiling together of cationic starch/negatively charged ion PAM/ alkali alumina has produced excellent ash content and kept effect, with the same chemical of independent interpolation Comparatively speaking.Outcome record is in table 12.
Table 12
The boiling of % ash retention and merging
% cationic starch charge neutralization rate PAM dosage (pound/ton) The weight ratio of starch/PAM Add separately/simultaneously Boiling together
16 0.5(0.25) 40/1 37 43
Numerical value in a bracket is kilogram/ton (kg/t).

Claims (8)

1, a kind of intermittent pulp proportioning, contain:
(a) soluble aluminum compound, its amount are 0.005-2.5 kilogram Al 2O 3/ metric ton dried paper and
(b) treated starch, by with at least a substitution value the aqueous solution of both sexes between the 0.01-0.2 or cationic starch and substitution value between 1wt%-80wt%, molecular weight at least 500,000 at least a nonionic or amphiprotic polyacrylamide, or the boiling and making together of positively charged ion or anionic polyacrylamide, precondition is:
(i) for the situation of selecting positively charged ion or non-ionic polyacrylamide, boiling is carried out being higher than under 7.0 the pH;
(ii) for the situation of selecting both sexes or anionic polyacrylamide, boiling makes the charge neutralization of cationic starch be less than 75%;
If (iii) the anionic polyacrylamide molecular weight is low, then boiling makes and is less than 75% cationic starch electric charge and is neutralized, if anionic polyacrylamide molecular weight height, then boiling makes and is less than 50% cationic starch electric charge and is neutralized, said low for being low to moderate 500,000, height is up to 8,000,000; With
(iv) the weight ratio of starch and polyacrylamide is higher than 2: 1.
2, the intermittent pulp proportioning of claim 1, wherein cationic starch is with the cation acrylamide boiling.
3, the intermittent pulp proportioning of claim 1, wherein cationic starch is with the boiling of negatively charged ion acrylamide.
4, claim 1,2 or 3 intermittent pulp proportioning wherein before adding treated starch, join soluble aluminum compound in the paper pulp.
5, claim 1,2 or 3 intermittent pulp proportioning, wherein starch is selected from W-Gum, yam starch and waxy corn starch.
6, wherein also there are colloid silica in claim 1,2 or 3 intermittent pulp proportioning.
7, wherein also there are anionic inorganic colloid in claim 1,2 or 3 intermittent pulp proportioning.
8, claim 1,2 or 3 intermittent pulp proportioning, wherein soluble aluminum compound is selected from Tai-Ace S 150, aluminate, aluminum nitrate, poly aluminium chloride and poly aluminium sulfate.
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KR100612162B1 (en) 2006-08-14
EP1025159A1 (en) 2000-08-09
JP2001521995A (en) 2001-11-13
EA200000474A1 (en) 2000-10-30
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SK286208B6 (en) 2008-05-06
EP1025159B1 (en) 2002-09-18
AU736084B2 (en) 2001-07-26
CA2307025C (en) 2008-01-08
PT1025159E (en) 2002-11-29
HUP0004165A2 (en) 2001-03-28
NZ504093A (en) 2001-03-30
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DE69808115T2 (en) 2003-04-30
CZ20001449A3 (en) 2001-02-14

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